Phosphorus derivatives of 1,2,4,5-tetrahydroxy benzene

ABSTRACT

Disclosed are benzobisphospholes of the formula:   WHEREIN: X represents halogen, NR2 where R is hydrogen, alkyl, or cycloalkyl, having up to 30 carbon atoms or aryl or aralkyl having up to 22 carbon atoms, pyrrolidino, piperidino or morpholino; Z is oxygen or sulfur or may be absent. These compounds are effective as anti-wear and anti-oxidant additives for lubricating oils. They also have flame retardant properties.

United States Patent n91 Dulog et al.

[ PHOSPHORUS DERIVATIVES 0F l,2,4,5-TETRAHYDROXY BENZENE [75] Inventors: Lothar G. Dulog, Sint Martens .Latem; Sylvain A. R. Dewaele,

Evergem, both of Belgium [73] Assignee: s.a. Texaco Belgium n.v., Brussels,

Belgium [22] Filed: Jan. 7, 1974 [2|] Appl No.: 431,250

Related US. Application Data [62] Division of Ser. No. 250,712, May 5. I972, Pat. No.

[56] References Cited UNITED STATES PATENTS 3,819,748 S/l974 Dulog et a1. 260/927 R [451 Oct. 7, 1975 Primary Examiner-Donald G. Daus Assistant Examiner-Jose Tovar Attorney, Agent, or FirmThomas H. Whaley; Carl G. Ries [57] ABSTRACT Disclosed are benzobisphospholes of the formula:

wherein:

X represents halogen, NR, where R is hydrogen, alkyl, or cycloalkyl, having up to 30 carbon atoms or aryl or aralkyl having up to 22 carbon atoms, pyrrolidino, piperidino or morpholino; Z is oxygen or sulfur or may be absent.

These compounds are effective as anti-wear and anti-oxidant additives for lubricating oils. They also have flame retardant properties 3 Claims, No Drawings PHOSPHORUS DERIVATIVES OF l,2,4,5-TETRAHYDROXY BENZENE CROSS-REFERENCE TO CO-PENDING APPLICATION This application is a division of coassigned patent application Ser. No. 250,712, filed May 5, 1972, now U.S. Pat. No. 3,819,748, issued June 25, 1974.

The present invention relates to compositions of matter classified in the art of chemistry as phosphorus derivatives of tetrafunctional aromatic compounds, to uses thereof and to methods of synthesizing the same. These compounds are 1,2d 4, d")-benzobis- (1,3,2-dioxaphospholes) and have the formula:

wherein:

X represents halogen, NR, where R is hydrogen, alkyl, or cycloalkyl, having up to 30 carbon atom or aryl or aralkyl having up to 22 carbon atoms, pyrrolidino, piperidino or morpholino; Z is oxygen or sulfur or may be absent.

These compounds are effective as anti-wear and antioxidant additives for lubricating oils. They also have flame retardant properties.

The starting material for preparing these compounds is 1,2,4,S-tetrahydroxybenzene, a practical synthesis of which is described in commonly assigned patent application Ser. No. 92,139, filed Nov. 23, 1970, now U.S. Pat. No. 3,780,114.

The compounds of the invention can be prepared by reacting 1,2,4,5-tetrahydroxybenzene (THB,1) by a series of reactions which may be summarized as follows:

When THE (1) is heated with a large excess of PCl and a small amount of water, the bischloridite (11) is obtained in 78-84 percent yield. The pure THE (1) can be replaced by the mixed crystals of THE (1) and tetrahydrofuran (THF), described in U.S. Pat. application Ser. No. 92,139, filed on Nov. 23, 1970, now U.S. Pat. No. 3,780,] 14, giving 11 in percent yield. The details are given in Examples 1 and 2. Table 1 contains several examples of runs. The bischloridite 11 can be converted into amides as shown below.

The reaction of THE (1) with POCl does not afford the expected bischloridate (IV). Therefore, IV was prepared in two other ways. First, the bischloridito 11 can be chlorinated in CCL, giving a solution of 111 and secondly, THB (1) can be converted into 111 by reaction with PCl in CCl When the solution of 111 is treated with acetone at room temperature, the bischloridate (1V) is obtained as an insoluble material. The overall yield by the transformations THE (1) ll lll 1V is 76.5 percent and by the sequence THE (1) -11] lV it is 54-69 percent. Both methods are described in Examples 4 and 5. Tables 11 and 111 (Examples 6 and 7) contain data of individual runs. The bischloridate (1V) can be converted into amides (see below).

Also the bisthiochloridate V cannot be prepared directly from THB (1) and PSCl because the two compounds do not, unexpectedly, react with each other. Therefore it was necessary to use the bischloridite (11) as a starting material for its preparation. A procedure was elaborated whereby the bischloridite (11) is treated with an excess of PSC1 and a catalytic amount of Et N. By this way, the bisthiochloridate (V) is obtained in an 82-88 percent yield. See also Example 8 and Table IV (Example 9). The overall yield for the conversion THE (1) 11 V in this way is 64-75 percent. The bisthiochloridate V has been converted into amides (see below).

The preparations of the amides derived from the bischlorides, 11, 1V and V are summarized in Tables V (Example 10), V1 (Example l I and Vll (Example 12), respectively. Generally these amides (V1, Z=O,S or absent) are prepared by reaction of the acid chloride (11, 1V or V) with four equivalents o o sc| s 0 45 Cl-P P-Cl -b m P P Pcl PSCI u 3 v U Cl HO OH o 0 Cl ct om of a primary or a secondary amine R NH in an inert solvent (like ether, benzene or mixtures thereof) at room temperature (Method A) (reaction 1 Half of the amine R NH can be replaced by a tertiary amine like triethylamine, Et N or pyridine (Method B). After mixing of the reagents, a precipitate of the amine hydrochloride R NHHCl (or Et N-HCI or pyridine hydrochloride) is formed and the amide (Vi) remains in solution. The amine hydrochloride is filtered off and the product Vl can be isolated by evaporation of the solvent. The yields of the crude products vary between 45 and 100 percent for the bisamidites (VI, Z is absent) Table V (Example between 62 and 94 percent for the bisamidates (VI, Z=O) Table [I (Example I l) and between l9 and 100 percent for the bisthioamidates (VI, Z=S) Table V" (Example 12). The bisthioamidates (VI, Z=S) also were obtained by heating a bisamidite (VI, Z is absent) with sulfur at 150C (equation 2).

(Z is absent) Vr From Table VI] (Example l2), it can be seen that the products prepared in this way (method C) were obtained in smaller yields and in lower purity than the bisthioamidates (VI, Z==S) prepared according to equation 1 (methods A and B).

EXAMPLE I THB (40 g), PCl (400 ml) and water (1.6 ml) were placed in a vessel provided with a nitrogen gas inlet, a sealed stirrer and an effective cooler. The vessel was protected against moisture by CaC'l -tubes and a slow stream of nitrogen was passed through the apparatus. The liquid was heated to the boiling point under stirring and refluxed for about 16 hours. After this period, the HCl evolution usually is complete. To the hazy solution Et N was added gradually at 70C (between 1.7 and 3.4 ml) until the solution became clear with a precipitate formed. This liquid was decanted at 70C and allowed to cool in a well closed flask to exclude moisture and air. The crystalline solid, the bischloridite (II) (85.5 g, 76 percent, mp l 32-l44C) was filtered off in a glovebox under dry nitrogenv A second crop was obtained from the filtrate upon further cooling (6. l g, 8 percent, mp l24-l34C). Upon recrystallization (from ben zene) the mp rises to l4ll44C.

EXAMPLE 2 In a three-necked flask, equipped with a nitrogen inlet, sealed stirrer and a reflux condenser, provided with a CaCl tube, were placed 69.5 g THB (l)-THF crystals, l.2 g (0.07 mole) H 0 and 300 ml (471 g, 3.42 moles) freshly distilled PCl Stirling and heating were started. The THB (l)-THF crystals dissolved after about 30 min t s. Refluxing of the mixture was continued for l6 hours, whereafter HCl evolution stopped. The solution contained a white haziness.

To the hot mixture was added a few drops to l ml of EtgN or pyridine after which it was refluxed for a few more minutes until the haziness coagulated to an oily precipitate. The liquid was decanted from the precipitate and allowed to cool. The bischloridite (II, 32.6 g) was obtained as white crystals of mp ll8l24C. A second crop (20.6 g) was obtained after reducing the amount of PCI;, to half of its original value. A third crop (3.3 g) was obtained in the same way, giving a total i ld of 56.5 g (85.2 percent).

1 The yield was calculated for crystals with a THF content of 50 percent.

P P (2) R N/ EXAMPLE 3 TABLE I Preparation of Bischloridite (ll) Run Procedure Bischloridite Yield (ll) mpC percent 1 As in Example 1 using l32-l44 76 40 g (0.28 mole) THE (1), l24-l44 8 628 g (400 ml, 4.56 moles) (note l) PCl L6 g (89 mmoles) H 0 and 1.5 g (2.08 ml. 13.6 mmoles) Et;,N 2 As in Example I using 130-134 69 59.5 g 0.42 mole) THB (n l26-l33 as 935 g (595 ml, 6.80 moles) PCL;v 2.4 g (0. l3 mole) H 0 and 2.95 g (4 ml, 27 mmoles) Et N 3 As in Example 2, using 9.3 g llB-l24 84 THB (l)-THF crystals 78.5 g impure 2i (50 ml, 0.57 mole) PCL fraction 0.2 g ll mmoles) H 0 and 2-3 drops Et N 4 As in Example 2 using 695g white 85 THB (l)THF'Crystals, l.2g crystals (0.07 mole) H O, WI 3 (300 ml, 3.42 moles) PC'l l ml pyridine l )Rccrystallization of samples from benzene raised the mp to Lil-144C.

EXAMPLE 4 In a two-necked 500 ml flask, provided with a gas inlet tube and a reflux condenser which carried a CaCl tube, was placed l() g (36.9 mmoles) bischloridite (II) and 360 ml CC]... After dissolution of the solid, the flask was cooled in an ice bath, the solution stirred magnetically and C1 gas, dried over concentrated H 50 was bubbled through the solution until it escaped from the CaCl tube. The ice bath was then removed and when the solution had warmed up to room temperature, dry N gas was bubbled through the solution to blow out the Cl, gas left. Some precipitate was filtered off and to the filtrate was added 5.2 g (6.6 ml, 90 mmoles) acetone, which was dried before over Na After standing overnight in a flask protected with a CaCl tube, the bischloridate (lV) which had formed as a white precipitate was filtered off in a dry glove-box under nitrogen (9.5 g, 85 percent). It melted at 235C (dec).

EXAMPLE 5 5 g (35 mmoles) THB and l8.3 g (87 mmoles) PCl were brought together in a 500 ml three-necked flask provided with a N gas inlet, a sealed mechanical stirrer and a reflux condenser protected with a CaCl tube. To this mixture was added 200 ml CCl whereupon'a vigorous reaction started. When the reaction became less vigorous the mixture was refluxed for 4 days. A'preeipitate was filtered off at room temperature and to the filtrate was added 5.l g (6.5 ml, 88 mmoles) acetone. After standing overnight the bischloridate (IV) (7.3 g, 69 percent) was filtered off as a slightly yellow precipitate.

EXAMPLE 6 TABLE ll Conversion of the Bischloriditc (ll) into the Bischloridate (V) Run Procedure Bischloridate Yield (IV) mp percent 5 As in Example 4 using 235-242 63 2.4 g (5.] mmoles) ll, (dec) 45 ml CCl and L2 g (20.7 mmoles) acetone 6 As in Example 4 using 235 (dec) 85 lt) g (36.9 mmoles) ll, 360 ml CCl, and 5.2 g (90 mmoles) acetone 7 As in Example 4 using 210-215 91 46 g (0.17 mole) ll, (den) 550 ml CCl and 2|.7g (0.38 mole) acetone ""l'he product is suluhlc in POCI and in THF "'The product cannot be recrystallized from acetone.

EXAMPLE 7 TABLE III Reaction of THB (l) with PCI, Run Procedure Bischloridatc Yield (IV) percent 8 As in Example 5 using Slightly 69 5 g [35 mmoles) THB ([1. yellow solid I83 g (87 mmoles) PCl- 200 ml CCl, 5.] g (6.5 ml, 88 mmoles) acetone. 9 As in Example 5 using White powder 54 2U.l g (0.24 mole) THB (I). 73.2 g (0.35 mole) PCl 75(ln1lCCl 203g 25.6 ml. 0.35 mole) acetone.

'Bcfore the acetone was added the solution cuutained the histrichloridale ("II as shown by the IR spectra.

EXAMPLE 8 Preparation of the Bisthioehloridate (V) In a three-necked flask provided with a N gas inlet, a sealed stirrer and a reflux condenser that carries a CaCl tube at the top are mixed together [0 g (36.9 mmoles) bischloridite (II), 37.2 g (22.8 ml, 219 mmoles) PSCL, and 0.18 g (0.25 ml, L63 mmoles) Et N under nitrogen. The mixture is heated under reflux for IS hours giving a clear brown solution and an oil that sticks on the walls of the flask. The hot solution is decanted from the oil and cooled in a refrigerator. The bisthiochloridate (V, 10.2l().9 g, 82-88 percent) is obtained as a white to slightly yellowish crystalline compound of melting point l45-l60C.

EXAMPLE 9 TABLE IV Reaction of the Bisehloridite (II) with PSCL Run Procedure Bisthioehloridatc Yield (V)mpC percent 10 As in Example 8 using 145-160 82 10 g (36.9 mmoles) ll, 37.2 g (219 mmoles) PSCI and 018 g L63 mmoles) Et,,N I] As in Example 8 using l37-l55 88 23.9 g (88 mmoles) ll, 89.6 g (529 mmoles) PSCl and 0.43 g (4127 mmoles) Et N EXAMPLE 10 TABLE V Preparation of Bisamidites (VI, 2 is absent) Method 0! Yield Melting Point Preparation (72 C) NHCH A 62 140-441 NHC H, A'-' 83 l85-l86 NHC H A 85 [Ob-I08 NH-nC,H,, A I00 (oil) NH-tCM, B 87 l58-l6t) NH-nC H A 62 (oil) NH-cyclo C t-l B 63 160-162 Nit-c m, A s5 90. 5-9l NHC H B 83 l52-l54 NH-pC H CH B 96 I64 NH-pc H nC H 8 I00 (oil) N(CH A an l63-l67 N(C s)-; B 90 l23-l24 N( nC 7 J: A 92 89-91 N( nC,H A 92 7t -77 N3 pyrrolidino A 64 l6()23(l (doe) NC) piperidino A 83 182-184 N O morpholino A 45 l94-l97 L/ Primene SI-R B (oil) The amounts of amine per mole of bischloridite (ll) are: Method A 4 moles of amine R NH Method B 2 moles of amine R NH 2 moles Et N The reaction was carried uut at WC "Primcne XIR is a trade name for a tertiary ulkyl primary amine. sold by Rohm and Hans Inc.

ExAMPLE ll EXAMPLE l2-Continued TABLE VI TABLE VII Preparation of the Bisamidates (VI. Z=(l) Preparation of the Bisthioamidates (VI, Z=S

Method of Yield (/r Melting Point Method of Yield Melting Point Preparation ("C 5 Preparation (7%) ("C) N C 'H A 8! 194-[96 NiiicjHli: B 62 106 N O morpholino A 57 m N( n( .H. B 88 (oil) NHp-Ed-ik l-I B 99 (oil) Prime 100 (mu Primene tiLR B 83 1854 86 10 The amounts of amine per molt: of bisthiochloridate V are: Method A 4 moles amine R.;NH Method B 2 moles amine R,NH. 2 moles Et N In Method C the ""Ihc amounts ofuminc per mole of bischloridatu (IV) are: Method Au 4 moles himmidim (VI 2 k 3mm) N "when with Wu mm of sum" m 50C :imiiie HNR2 Method B 2 moles amine HNIL, 2 moles Et N mnckm was Carr-led um m w m F XI'R a name {0r 3 alkyl primary amine mm by Rohm "Primcnc Xl-R is a trade name for a tertiary zilkyl primary umine sold by Rnhm MT and Haas. Inc.

The reaction mixture had to be heated to the boiling point for 3 to 6 hours.

Representative compounds according to the invention were tested by the Navy Wear Test, the Rotary Bomb Oxidation Test, the Mean Hertz boad Test, the Rust Test and the Copper Strip Corrosion Test. The test data demonstrated load carrying and anti-oxidant ro rties r th e m unds. EXAMPLE 12 P e 0 P While the present invention has been illustrated mainly with reference to benzobisphospholes which are TABLE VII prepurmion f the Bishioumidmes =s unsubstituted on the aromatic nucleus, it will be under- Mcflmyflf Yleld Mel'mg stood that the same is applicable also to analogous Preparation (7%) (C) compounds having on this nucleus various non- C fl t 19 277-283 interfering substituents such as alkyl, halogen, aryl, alk- '7 2 :2 iiiiii i A l5] |54 What is claimed is: H-IQ A 69 253 (dcc) l. A compound of the formula: Nil-QM, A 100 IU4-l06 Nl-I-cyclo C.,H A 50 2U62l0 NH-nC,,I-I,,, B 99 95-97 NHC H, A 94 20i-204 NH-pCJ'LCH, A 99 226-237 NH-PCJLCWHQ B I00 (in N(CH,), A 51 281-284 N C,H, A 84 245-246 N n-C,H, C 86 i74-is5 A 97 I'm-I96 M n-(5H, A 33 96-100 N( cyclo-C-H n 2 A 100 265-270 h i N(nC H B 26 69-71 40 X represents pyrrolidino, piperidino or morpholino; 3 pymlldlm C 325-347 Z is oxygen, sulfur or is absent.

A 89 242446 2. The compound according to claim 1 wherein Z is 4 sulfur and X is pyrrolidino, piperidino or morpholino. N p|perid|no C 42 210-260 3 Th e compound according to claim 1 wherein Z is A 50 228-23 45 oxygen and X is pyrrolidino, piperidino or morpholino. 

1. A COMPOUND OF THE FORMULA:
 2. The compound According to claim 1 wherein Z is sulfur and X is pyrrolidino, piperidino or morpholino.
 3. The compound according to claim 1 wherein Z is oxygen and X is pyrrolidino, piperidino or morpholino. 